EP1335696B1 - Colorant enzymatique - Google Patents

Colorant enzymatique Download PDF

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Publication number
EP1335696B1
EP1335696B1 EP01996352A EP01996352A EP1335696B1 EP 1335696 B1 EP1335696 B1 EP 1335696B1 EP 01996352 A EP01996352 A EP 01996352A EP 01996352 A EP01996352 A EP 01996352A EP 1335696 B1 EP1335696 B1 EP 1335696B1
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Prior art keywords
amino
bis
agent according
acid
und
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German (de)
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EP1335696A2 (fr
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Astrid Kleen
Bianca Frauendorf
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE10116759A external-priority patent/DE10116759A1/de
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/447—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof containing sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A61K8/604—Alkylpolyglycosides; Derivatives thereof, e.g. esters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/66—Enzymes

Definitions

  • the present invention relates to agents for dyeing keratinic fibers, which contain, inter alia, at least one enzyme which can catalyze the oxidation of the dye precursors and a combination of active ingredients of at least one sugar surfactant and a reducing agent, the use of these agents for dyeing keratinic fibers and various methods of dyeing keratinic fibers with these agents.
  • Human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.
  • dyeing or tinting agents which contain so-called direct drawers as a coloring component. These are dye molecules that grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable nuance shift or even a visible "discoloration" occurs much more quickly.
  • oxidation colorants For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidants or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes.
  • the oxidation stains are characterized by excellent, long lasting staining results.
  • a mixture of a larger number of oxidation dye precursors must usually be used; In many cases, direct dyes are still used for shading.
  • the oxidative development of the dyeing can in principle be carried out with atmospheric oxygen.
  • a chemical oxidizing agent is used.
  • Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.
  • German Offenlegungsschrift DE-OS-21 55 390 describes an enzyme-activated, oxidative hair dyeing process in which small amounts of H 2 O 2 are used in combination with a peroxidase.
  • EP-A1-0 310 675 discloses enzymatic hair treatment compositions containing at least a two-electron reducing oxidase utilizing oxygen as the acceptor.
  • EP-B1-0 548 620 Enzymatic hair dyes are described in which the oxidation of the dye precursors is catalyzed by the use of a peroxidase.
  • the technique of readily oxidizable dye precursors, as well as the hitherto described enzymatic color development, has the disadvantage that, in comparison with the conventional processes, in particular with regard to the intensity, the gloss and the fastness properties of the dyeings, poorer results are achieved.
  • the enzymatic hair dyes of the prior art also have the disadvantage that relatively high amounts of enzyme are needed to obtain conventional staining results.
  • the present invention is therefore based on the task of providing enzymatic colorants for keratinic fibers which, even with the use of minimal amounts of enzyme and / or dye, fulfill the requirements imposed on colorants to a high degree. It is a further object of the present invention to provide colorants that are gentle to the skin and hair.
  • keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair.
  • the colorant contains at least one developer component.
  • developer components are usually primary aromatic amines having a further, located in the para or ortho position, free or substituted hydroxy or amino, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,
  • C 1 -C 4 -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals.
  • C 1 -C 4 -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group.
  • a C 1 - to C 4 -hydroxyalkyl group a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned.
  • a 2-hydroxyethyl group is particularly preferred.
  • halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred.
  • the other terms used are derived according to the invention from the definitions given here.
  • nitrogen-containing groups of the formula (E1) are in particular the amino groups, C 1 to C 4 monoalkylamino groups, C 1 to C 4 dialkylamino groups, C 1 to C 4 trialkylammonium groups, C 1 to C 4 monohydroxy groups alkylamino groups, imidazolinium and ammonium.
  • Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N- bis ( ⁇ -hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (
  • Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine and N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) - N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) me
  • Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) - 1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.
  • Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxy-methylamino-4-amino -phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol , 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol , 4-amino-2 - ((diethylamino) methyl) phenol and their physiologically acceptable
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2 - ((diethylamino) methyl) phenol.
  • the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.
  • the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.
  • Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196 such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- ( ⁇ -methoxyethyl) amino-3- amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
  • Preferred pyrimidine derivatives are, in particular, the compounds which are known in the German Patent DE 2 359 399 , of the Japanese Laid-Open Patent Publication JP 02019576 A2 or in the published patent application WO 96/15765 described as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2, 5,6-triaminopyrimidine.
  • Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969 . WO 94/08970 .
  • EP-740931 and DE 195 43 988 such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chloro- benzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino 1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-di
  • the pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
  • compositions according to the invention may contain cationic dye precursors of the coupler and / or developer type, as described, for example, in the published patent applications WO-A1-99 / 03,819 . WO-A2-99 / 03 834 . WO-A1-99 / 03,836 . WO-A1-99 / 48,856 . WO-A1-99 / 48 874 . WO-A1-99 / 48,875 . WO-A2-00 / 42 971 . WO-A1-00 / 42 979 . WO-A1-00 / 42 980 . WO-A1-00 / 43,356 . WO-A1-00 / 43 367 .
  • Particularly preferred cationic dye precursors are [2- (2 ', 5'-diamino-phenoxy) -ethyl] -diethyl-methyl-ammonium chloride, [2- (4'-amino-phenylamino) propyl] trimethylammonium chloride, [4- (4'-Amino-phenylamino) pentyl] diethyl (2-hydroxyethyl) ammonium chloride, 1 - ⁇ [5'-amino-2 '- (2 "hydroxyethylamino) phenylcarbamoyl] -methyl ⁇ -1,4-dimethylpiperazin-1-ium chloride, 1,4-bis-1- ⁇ 3- [3 '- (2 ", 5" diamino-phenoxy) -propyl] -3H-imidazol-1-ium ⁇ butane dichloride, 1,3-bis [3 '- (2 ", 5" diamino-phenoxy) -propyl
  • colorants which contain at least one coupler component are preferred according to the invention.
  • coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used.
  • Suitable coupler substances are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 -methylpyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3 -aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.
  • coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, minor amounts may contain other components, as far as these do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.
  • the dye precursors are amino compounds
  • the known acid addition salts can be prepared therefrom in the customary manner. All statements of this document and accordingly the scope claimed are therefore based on both the present in free form compounds and their water-soluble, physiologically acceptable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.
  • the oxidation dye precursors are contained in the agents according to the invention preferably in amounts of 0.01 to 20 wt .-%, preferably 0.5 to 5 wt .-%, each based on the total agent.
  • indoles and indolines which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring.
  • these groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.
  • the colorants contain at least one indole and / or indoline derivative.
  • Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
  • the indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for.
  • hydrochlorides sulfates and hydrobromides are used.
  • the indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.
  • the indoline or indole derivative in hair dyes in combination with at least one amino acid or an oligopeptide.
  • the amino acid is advantageously an ⁇ -amino acid;
  • Very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
  • the agents according to the invention for obtaining the desired dyeing effects may further comprise at least one substantive dye.
  • Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • Preferred substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52
  • Preferred cationic substantive dyes of group (iii) are in particular the following compounds:
  • the compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of the group (ii).
  • the agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.
  • preparations according to the invention may also contain naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, sedre and alkano root.
  • naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, sedre and alkano root.
  • the agents according to the invention contain as second compelling component at least one enzyme which can catalyze the oxidation of the dye precursors.
  • the enzymes to be used which directly oxidize the dye precursors with the help of atmospheric oxygen, are the laccases ( EC-No. 1.10.3.2 ), the tyrosinases ( EC-No. 1.10.3.1 ), Ascorbate oxidase ( EC-No. 1.10.3.3 ), the bilirubin oxidases (BC No. 1.3.3.5) and phenol oxidases of the type Acremonia, Stachybotrys or Pleurotus.
  • the laccases are very particularly preferred according to the invention enzymes.
  • the enzymes can be incorporated into the colorant itself; but they are preferably formulated separately from the dye precursors and mixed with the actual colorant only immediately before use. If the enzymes are incorporated into the colorant as a 1-component system, it is preferred according to the invention to formulate the system in the absence of air.
  • the dyeing agent free of blowing agents, that is not to make up as a foam formulation.
  • the enzyme is preferably used in an amount of 0.0001 - 1 wt .-%, based on the protein amount of the enzyme and the total colorant.
  • the agents according to the invention contain as third obligatory component (C) at least one sugar surfactant.
  • the sugar surfactant is an alkyl or alkenyl oligoglycoside.
  • These sugar surfactants are known nonionic surfactants according to formula (II), R 1 O- [G] p (II) in which R 1 is an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature is here on the review by Biermann et al. in Starch / charity 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) and J. Kahre et al. in S ⁇ FW Journal Heft 8, 598 (1995).
  • the alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides and stands for a number between 1 and 10.
  • the value p for a given alkyloligoglycoside is an analytically determined arithmetical variable, which is usually a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 1 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above.
  • Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
  • the sugar surfactant is a fatty acid N-alkylpolyhydroxyalkylamide, a nonionic surfactant of the formula (III), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • a reducing sugar with ammonia
  • an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • H. Kelkenberg An overview of this topic by H. Kelkenberg can be found in Tens. Surf. Det. 25 , 8 (1988).
  • the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IV):
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R 3 is hydrogen or an alkyl group and R 2 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or whose technical mixtures.
  • fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • the sugar surfactant is contained in the agents used according to the invention preferably in amounts of from 0.1 to 20% by weight, based on the total agent. Amounts of 0.5 to 5 wt .-% are particularly preferred.
  • the agents according to the invention contain a reducing agent.
  • reducing agents which are preferred according to the invention are sodium sulfite, ascorbic acid, thioglycolic acid and derivatives thereof, sodium thionite, alkali metal citrate salts and N-acetyl-L-cysteine.
  • Very particularly preferred reducing agents are alkali metal citrate salts, in particular sodium citrate, and N-acetyl-L-cysteine.
  • N-acetyl-L-cysteine is a most preferred alkalizing agent.
  • the agents according to the invention may contain fatty acid partial glycerides.
  • These fatty acid partial glycerides are monoglycerides, diglycerides and their technical mixtures. With the use of technical products production reasons may still contain small amounts of triglycerides.
  • the partial glycerides preferably follow the formula (V), in which R 4 , R 5 and R 6 independently of one another are hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups is hydrogen.
  • the sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25.
  • R 4 is an acyl radical and R 5 and R 6 are hydrogen and the sum (m + n + q) is 0.
  • Typical examples are mono- and / or diglycerides based on caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic , Elaeostearic acid, arachidic acid, gadoleic acid, Behenic acid and erucic acid and their technical mixtures.
  • oleic acid monoglycerides are used.
  • the fatty acid partial glyceride is preferably contained in the agents used according to the invention in amounts of 0.1-20% by weight, in particular 0.5-2% by weight, based on the total agent.
  • the teaching according to the invention also encompasses embodiments in which the agents according to the invention comprise a plurality of sugar surfactants and / or several fatty acid partial glycerides.
  • the agents according to the invention may further comprise at least one thickener.
  • thickeners there are no fundamental restrictions. Although in principle both organic and purely inorganic thickening agents can be used, the organic thickeners are preferred according to the invention.
  • the thickener is an anionic synthetic polymer.
  • Preferred anionic groups are the carboxylate and sulfonate groups.
  • anionic monomers from which the polymeric anionic thickeners may consist are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.
  • the acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt.
  • Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.
  • Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trade drawing Carbopol ® commercially. Also preferred is the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ® 11-80 commercially.
  • copolymers of at least one anionic monomer and at least one nonionic monomer are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, itaconic acid mono- and diesters, vinylpyrrolidone, vinyl ethers and vinyl esters.
  • Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C 1 - to C 6 -alkyl esters, as sold under the INCI declaration Acrylates Copolymers.
  • a preferred commercial product is, for example, Aculyn ® 33 from Rohm & Haas.
  • Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are in particular steareth-20 or ceteth-20.
  • Such copolymers are sold by Rohm & Haas under the trade name Aculyn ® 22 and by National Starch under the trade names Structure ® Structure 2001 ® 3,001th
  • Preferred anionic copolymers are also acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers.
  • a particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present.
  • This copolymer can also be present in crosslinked form, with crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide.
  • crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide.
  • crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide.
  • Such a polymer is contained in the commercial products Sepigel ® 305 and Simulgel® ® 600 from SEPPIC.
  • Polymers of maleic anhydride and methyl vinyl ether, in particular those with crosslinks, are preferred thickeners.
  • a cross-linked with 1,9-decadiene maleic acid-methyl vinyl ether copolymer is available under the name Stabileze® ® QM.
  • the thickener is a cationic synthetic polymer.
  • Preferred cationic groups are quaternary ammonium groups.
  • those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.
  • Suitable physiologically tolerated counterions X - include, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.
  • a particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37.
  • the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose.
  • Methylenebisacrylamide is a preferred crosslinking agent.
  • the homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight.
  • Such polymer dispersions are (under the names Salcare ® SC 95 50% polymer content, an additional component: Mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol (with a mixture of caprylic and capric acid INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name : PPG-1-trideceth-6) are commercially available.
  • nonionic thickeners of the polymeric fatty acid amide type as described, for example, in US Pat EP-A1-632083 or of EP-A2-959066 be revealed.
  • Copolymers having monomer units of the formula (VI) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C 1-4 -alkyl ester and methacrylic acid-C 1-4 -alkyl ester.
  • nonionic monomers preferably acrylamide, methacrylamide, acrylic acid-C 1-4 -alkyl ester and methacrylic acid-C 1-4 -alkyl ester.
  • the acrylamide is particularly preferred.
  • These copolymers can, as in the case of homopolymers described above, be crosslinked.
  • a copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer.
  • Such copolymers in which the monomers are present in a weight ratio of about 20:80 are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ® SC.
  • naturally occurring thickening agents are used.
  • Preferred thickening agents of this embodiment are, for example, nonionic guar gum.
  • both modified and unmodified guar gums can be used.
  • Unmodified guar gums are marketed under the trade name Jaguar ® C from Rhone Poulenc.
  • Modified guar gums preferred according to the invention contain C 1 to C 6 hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl.
  • Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides.
  • the degree of hydroxyalkylation which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gum free hydroxy groups, is preferably between 0.4 and 1.2.
  • modified guar gum are under the trade names Jaguar ® HP8, Jaguar ® HP60, Jaguar ® HP120, Jaguar DC 293 and Jaguar ® ® HP105 Rhone Poulenc commercially available.
  • biosaccharide gums of microbial origin such as scleroglucan gums or xanthan gums, vegetable exudate gums such as gum arabic, ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar, locust bean gum, pectins, Alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins.
  • nonionic, fully synthetic polymers such as polyvinyl alcohol or polyvinylpyrrolidone
  • thickeners can be used according to the invention.
  • Preferred nonionic, fully synthetic polymers are for example marketed by BASF under the trade name Luviskol ®.
  • the thickeners used are cellulose and / or cellulose derivatives, such as, for example, methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses.
  • Preferred hydroxyalkyl celluloses are, in particular, the hydroxyethylcelluloses, which are sold under the names Cellosize ® of the company Amerchol, Natrosol ® from Hercules or Culminal ® and Benecel ® Aqualon. Also suitable for this invention, the hydroxypropyl how they are marketed for example under the name Klucel ® by Hercules are.
  • Suitable carboxyalkyl are especially the carboxymethylcelluloses as sold under the names Blanose ® by Aqualon, Aquasorb ® and ambergum ® from Hercules and Cellgon ® from Montello.
  • the agents according to the invention also contain at least one nourishing polymer.
  • Nursing polymers include both natural and synthetic polymers which may be anionic, cationic, amphoteric or nonionic.
  • Cationic polymers are polymers which have groups in the main and / or side chain which may be “temporary” or “permanent” cationic.
  • “permanently cationic” refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are typically polymers containing a quaternary nitrogen atom, for example in the form an ammonium group.
  • Preferred cationic groups are quaternary ammonium groups.
  • those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.
  • Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ® LM 200), known polymers.
  • Gaffix ® VC 713 manufactured by ISP:
  • the copolymers of vinylpyrrolidone such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 available are.
  • cationic polymers are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic.
  • chitosan and its derivatives are preferred as Hydagen CMF ®, Hydagen HCMF ®, Kytamer ® PC and Chitolam ® NB / 101 are freely available commercially, for example under the trade names.
  • Chitosans are deacetylated chitins, which are commercially available in different degrees of deacetylation and different degrees of degradation (molecular weights). Their production is eg in DE 44 40 625 A1 and in DE 1 95 03 465 A1 described.
  • Particularly suitable chitosans have a degree of deacetylation of at least 80% and a molecular weight of 5 ⁇ 10 5 to 5 ⁇ 10 6 (g / mol).
  • the chitosan must be converted into the salt form. This can be done by dissolving in dilute aqueous acids.
  • Suitable acids are both mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid and organic acids, for example low molecular weight carboxylic acids, polycarboxylic acids and hydroxycarboxylic acids.
  • higher molecular weight alkyl sulfonic acids or alkyl sulfuric acids or organophosphoric acids are used, provided that they have the required physiological compatibility.
  • Suitable acids for converting the chitosan into the salt form are, for example, acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidinone-5-carboxylic acid, benzoic acid or salicylic acid. Preference is given to using low molecular weight hydroxycarboxylic acids, for example glycolic acid or lactic acid.
  • amphoteric polymers can be used as constituents as polymers for increasing the action of the active ingredient according to the invention.
  • amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO 3 H groups and are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO - or -SO 3 - groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer suitable is the acrylic resin commercially available as Amphomer ® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • polymer is beispeielsweise under the name Merquat ® 280 available Polyquaternium-22, which is a copolymer of dimethyldiallylammonium chloride and acrylic acid.
  • amphoteric polymers are those in the British Patent Application 2,104,091 , of the European Patent Application 47,714 , the European patent application 217 274 , of the European Patent Publication 283,817 and the German Offenlegungsschrift 28 17 369 mentioned compounds.
  • a preferred such polymer is beispeielsweise the product sold under the name Merquat ® 2001 by Calgon Polyquaternium-47.
  • the agents according to the invention may furthermore contain nonionogenic caring polymers.
  • the preparations used to comprise a plurality of, in particular two, different care polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.
  • the term "caring polymer” also means special preparations of polymers, such as spherical polymer powders.
  • Various methods are known for producing such microspheres from different monomers, for example by special polymerization processes or by dissolving the polymer in a solvent and spraying it into a medium in which the solvent can evaporate or diffuse out of the particles.
  • Suitable polymers are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides. Particularly suitable are those spherical polymer powders whose primary particle diameter is less than 1 micron.
  • Such products based on a polymethacrylate copolymer are, for example, under the trade name Polytrap ® Q5-6603 (Dow Corning) in the trade.
  • Other polymer powders eg based on polyamides (nylon 6, nylon 12) are with a particle size of 2-10 microns (90%) and a specific surface area of about 10 m 2 / g under the trade name Orgasol ® 2002 DU Nat Cos ( Atochem SA, Paris).
  • spherical polymer powders which are suitable for the purpose according to the invention are, for example, the polymethacrylates (Micropearl M) by NIKKOL SEPPIC or (Plastic Powder A), NIKKOL's Styrene-Divinylbenzene Copolymers (Plastic Powder FP), AKZO's Polyethylene and Polypropylene Powders (ACCUREL EP 400) or Silicone Polymers (Silicone Powder X2-1605) from Dow Corning or even spherical cellulose powders.
  • the polymethacrylates (Micropearl M) by NIKKOL SEPPIC or (Plastic Powder A)
  • NIKKOL's Styrene-Divinylbenzene Copolymers Plastic Powder FP
  • AKZO's Polyethylene and Polypropylene Powders ACCUREL EP 400
  • Silicone Polymers Silicone Polymers
  • the nourishing polymers are contained in the agents used according to the invention preferably in amounts of 0.01 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 2 wt .-%, are particularly preferred.
  • the dye precursors may be incorporated into a suitable aqueous vehicle.
  • suitable aqueous vehicle e.g. Creams, emulsions, gels or surfactant-containing foaming solutions, e.g. Shampoos, foam aerosols or other preparations suitable for use on the hair.
  • the colorants of the invention may further contain all known for such preparations active ingredients, additives and excipients.
  • the colorants contain at least one other surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable.
  • the person skilled in the art can optionally check a possible influence of the various surfactants on the activity of the enzyme system according to the invention by simple preliminary experiments.
  • the keratin fiber coloring agents employ a combination of anionic and nonionic surfactants or a combination of anionic and amphoteric surfactants.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,
  • zwitterionic surfactants can be used, in particular as cosurfactants.
  • Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO (-) or -SO 3 (-) group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
  • ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C 8 -C 18 -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12-18 acylsarcosine.
  • the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.
  • Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
  • alkyltrimethylammonium chlorides dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
  • cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®.
  • the products Armocare ® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehyquart® ® F-75 and Dehyquart® ® AU-35 are examples of such esterquats.
  • the alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • An inventively particularly suitable compound from this group of substances under the name Tegoamid ® S 18 commercial stearamidopropyl dimethylamine is.
  • cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
  • cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80.).
  • Glucquat ® 100 is, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
  • the compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.
  • both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
  • "normal” homolog distribution are thereby Mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts.
  • Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts.
  • the use of products with narrow homolog distribution may be preferred.
  • the agents according to the invention preferably contain at least one alkalizing agent.
  • alkalizing agents are ammonia, monoethanolamine, isopropylamine, isopropanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, especially sodium hydroxide or potassium hydroxide, and especially arginine, lysine and histidine.
  • colorants which comprise monoethanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide, and in particular arginine, lysine and histidine.
  • the colorants of the invention may preferably also contain a conditioning agent selected from the group consisting of cationic surfactants, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.
  • a conditioning agent selected from the group consisting of cationic surfactants, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.
  • conditioning active ingredients are silicone oils, in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated and quaternized analogs.
  • silicones examples include the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 and the commercial products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt. diquaternary polydimethylsiloxanes, quaternium-80).
  • conditioning active ingredients are paraffin oils, synthetically prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil.
  • suitable hair-conditioning compounds are phospholipids, for example soya lecithin, egg lecithin and cephalins.
  • preparations used according to the invention preferably contain at least one oil component.
  • Oil components which are suitable according to the invention are, in principle, all water-insoluble oils and fatty substances and mixtures thereof with solid paraffins and waxes. According to the invention, those substances whose solubility in water at 20 ° C. is less than 0.1% by weight are defined as water-insoluble.
  • the melting point of the individual oil or fat components is preferably below about 40 ° C. Oil and fat components that are at room temperature, d. H. may be liquid below 25 ° C, may be particularly preferred according to the invention. When using several oil and fat components and possibly solid paraffins and waxes, it is usually sufficient, however, if the mixture of oil and fat components and possibly paraffins and waxes meets these conditions.
  • a preferred group of oil components are vegetable oils.
  • vegetable oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil.
  • triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils.
  • a further, particularly preferred group according to the invention as oil component of usable compounds are liquid paraffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n- Decyl n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert
  • oil components are fatty acid and fatty alcohol esters.
  • the monoesters of the fatty acids with alcohols having 3 to 24 C atoms are preferred.
  • This group of substances are the products of the esterification of fatty acids having 6 to 24 carbon atoms such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z.
  • alcohols such as isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, for example in the pressure splitting of natural fats and oils.
  • Dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate and diol esters such as Ethylene glycol dioleate, ethylene glycol diisotridecanoate.
  • diol esters such as Ethylene glycol dioleate, ethylene glycol diisotridecanoate.
  • fatty alcohols having 8 to 22 carbon atoms can also be used as oil components according to the invention.
  • the fatty alcohols may be saturated or unsaturated and linear or branched.
  • the fatty alcohols are derived from preferably natural fatty acids, which can usually be based on recovery from the esters of fatty acids by reduction.
  • those fatty alcohol cuts which are produced by reduction of naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols.
  • the oil components are preferably used in amounts of from 0.05 to 10% by weight, in particular from 0.1 to 2% by weight, in the colorants according to the invention.
  • the enzyme preparation is mixed immediately before the dyeing of the hair with the preparation of the dye precursors.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 4 to 10, in particular from 6 to 9, very particularly from 7 to 8.5.
  • low-viscosity application preparations have proven to be particularly advantageous, which have a viscosity of less than 3000mPas (Brookfield, spindle 4, 20 rev / min, 20 ° C).
  • the application temperatures may range between 10 and 50 ° C, preferably between 20 and 35 ° C.
  • the fibers after treatment with the composition according to the invention may be subjected to an aftertreatment with a solution which contains small amounts of hydrogen peroxide.
  • the solution can be formulated, for example, in the form of a shampoo or a conditioner.
  • such aftertreatment agent contains hydrogen peroxide in concentrations between 0.01 and 0.5 wt .-%.
  • the agents in particular the separately prepared enzyme preparation, free from antioxidants and / or complexing agents as they can block the action of the enzymes.
  • a second object of the present invention is a process for dyeing keratinic fibers, in which an agent according to the invention is applied to the fibers and rinsed off again after a contact time.
  • a third aspect of the present invention is a process for dyeing keratinic fibers, in which an agent according to the invention is used, wherein in a first step a preparation comprising the components (A), (C) and (D) is applied to the fibers, the fibers are optionally rinsed after a contact time and, in a second step, a preparation comprising component (B) is applied to the fibers.
  • Also suitable as being suitable according to the invention has been found to be a process in which, in a first step, the fibers are treated with a preparation comprising component (B), the fibers are optionally rinsed after an exposure time, and subsequently a preparation containing the components (A), (C) and (D) is applied.
  • a fourth subject of the present invention is the use of the agents according to the invention for the oxidative dyeing of keratinic fibers.
  • Carbopol ® 934 1.0 Eumulgin ® B2 0.2 Eumulgin ® B1 9 0.2 Plantacare ® 1200 UP 0.5 Lame Soft ® PO65 0.2 Tri-Kaliumcitratdihydrat 0.5 2,4,5,6-tetra-sulfate 0.7 p-toluenediamine sulphate 0.4 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine sulfate 0.1 3-methyl-4-aminophenol 0.5 2-methyl 0.5 2,7-dihydroxynaphthalene 12:16 4-chlororesorcinol 0.1 2-amino-3-hydroxypyridine 0.5 Rodol 9R Base 0.1 histidine 0.2 Monoethanolamine ad pH 7 water ad 100 9 cetylstearyl alcohol with ca. 12 EO units (INCI name: Ceteareth-12) (Cognis)
  • a laccase from Rhus vernificera from Sigma was used.
  • the activity of the laccase is defined according to the manufacturer's instructions such that one unit [1U] corresponds to the amount of laccase which has a ⁇ A 530 of 0.001 per minute at a pH of 6.5 and 30 ° C in 3 ml of a reaction solution with syringaldazine Substrate yields.
  • the laccase was used in each case in such an amount, which has an activity of 280 000U under the above conditions.
  • an ascorbate oxidase from Cucurbita species from Roche-Diagnostics was used.
  • the activity of the ascorbate oxidase is defined such that one unit [1U] corresponds to the amount of ascorbate oxidase present in a phosphate buffer solution (KH 2 PO 4 , 0.1 mol / L; Na 2 HPO 4 , 4 mmol / L EDTA, 0.5 mmol / l) catalyzes the oxidation of 1 ⁇ mol L-ascorbic acid within one minute at pH 5.6 and 25 ° C (as defined by the commercial products of Roche Diagnostics). Detection is spectroscopically based on the decrease in absorbance at 245nm.
  • the ascorbate oxidase was used in each case in an amount which has an activity of 100,000 U under the conditions mentioned above.
  • a bilirubin oxidase from Myrothecium verrucaria from Sigma was used.
  • the activity of bilirubin oxidase is defined such that one unit [1U] corresponds to the amount of bilirubin oxidase which catalyzes the oxidation of 1 ⁇ mol bilirubin within one minute at pH 8.4 and 37 ° C.
  • the bilirubin oxidase was used in each case in an amount which has an activity of 1 000 U under the conditions mentioned above.
  • 60 g of the respective dyeing gel 1 to 11 were mixed with 10 ml of a buffered (by KHPO 4 / KH 2 PO 4 ) to pH 7 solution containing the ac enzymes in the activities mentioned under point II).
  • the mixture was applied to human hair (Kerling, natural white, 4 g of colorant per 0.5 g of hair), incorporated and for 30 min. left at room temperature. The hair was then rinsed and dried.
  • hue laccase ascorbate bilirubin Dyeing gel 1 russet autumn brown autumn brown Dyeing gel 2 herbstrot maroon herbstrot Dyeing gel 3 garnet garnet garnet Coloring gel 4 medium brown tan medium brown Dyeing gel 5 dark brown medium-dark brown medium-dark brown Dyeing gel 6 light golden brown golden brown Dyeing gel 7 hazel tawny tawny Dyeing gel 8 red copper copper copper gold Dyeing gel 9 copper copper brown copper gold 1 Dyeing gel 10 dark purple dark purple dark purple Dyeing gel 11 black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black black

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Claims (22)

  1. Agent pour teindre les fibres kératiniques contenant dans un véhicule acceptable sur le plan cosmétique
    (A) au moins un produit précurseur de colorant
    (B) au moins une enzyme, qui peut catalyser l'oxydation des produits précurseurs de colorant, choisie parmi les laccases (EC-N°1.10.3.2), les tyrosinases (EC-N°1.10.3.1), l'ascorbate oxydase (EC-N°1.10.3.3), les bilirubine oxydases (EC-N°1.3.3.5) ainsi que les phénol oxydases du type Acremonia, Stachybotrys ou Pleurotus.
    (C) au moins un tensio-actif glucidique, choisi dans le groupe qui est formé par
    - les alkyl- et alcényl-oligoglycosides et
    - les N-alkyl-polyhydroxyalkylamides d'acide gras et
    (D) au moins un agent réducteur.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient en tant que produit précurseur de colorant (A) au moins un composant révélateur.
  3. Agent selon l'une quelconque des revendications 1 ou 2, caractérisé en ce qu'il contient en tant que produit précurseur de colorant (A) au moins un dérivé indole et/ou indoline.
  4. Agent selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient au moins un composant de couplage.
  5. Agent selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient en plus au moins un colorant montant directement sur les fibres.
  6. Agent selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient en tant qu'agent réducteur, un sel citrate de métal alcalin, en particulier le citrate de sodium, et/ou la N-acétyl-L-cystéine.
  7. Agent selon la revendication 6, caractérisé en ce qu'il contient en tant qu'agent réducteur, la N-acétyl-L-cystéine.
  8. Agent selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il contient en plus au moins un glycéride partiel d'acide gras.
  9. Agent selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'il contient en plus au moins un épaississant.
  10. Agent selon la revendication 9, caractérisé en ce que l'épaississant est un polymère anionique ou non ionique.
  11. Agent selon l'une quelconque des revendications 9 ou 10, caractérisé en ce qu'il contient en tant qu'épaississant, au moins une cellulose et/ou un dérivé de cellulose.
  12. Agent selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il contient en plus un polymère de soin.
  13. Agent selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'il contient au moins un tensio-actif supplémentaire.
  14. Agent selon la revendication 13, caractérisé en ce qu'il contient un tensio-actif non ionique ou un tensio-actif amphotère.
  15. Agent selon l'une quelconque des revendications 1 à 14,
    caractérisé en ce qu'il contient au moins un agent d'alcalinisation.
  16. Agent selon la revendication 15, caractérisé en ce qu'il contient en tant qu'agent d'alcalinisation, la monoéthanolamine, l'isopropylamine, l'isopropanolamine, le 2-amino-2-méthylpropan-1-ol, l'arginine, l'histidine, ou un hydroxyde de métal alcalin, en particulier l'hydroxyde de sodium ou l'hydroxyde de potassium.
  17. Agent selon l'une quelconque des revendications 1 à 16, caractérisé en ce qu'il présente une valeur de pH de 4 à 10, en particulier de 6 à 9, de manière tout particulièrement préférée de 7 à 8,5.
  18. Agent selon l'une quelconque des revendications 1 à 17, caractérisé en ce qu'il constitue une préparation de faible viscosité ayant une viscosité inférieure à 3 000 mPas (Brookfield, broche 4, 20 tr/mn, 20°C).
  19. Procédé pour teindre les fibres kératiniques dans lequel un agent selon l'une quelconque des revendications 1 à 18 est appliqué sur les fibres et éliminé de nouveau par rinçage après une durée d'action.
  20. Procédé pour teindre les fibres kératiniques, dans lequel est employé un agent selon l'une quelconque des revendications 1 à 18, où dans une première étape, une préparation, contenant les composants (A), (C) et (D) est appliquée sur les fibres, les fibres étant éventuellement rincées après une durée d'action, et dans une deuxième étape une préparation contenant le composant (B) est appliquée sur les fibres.
  21. Utilisation d'un des agents selon les revendications 1 à 18 pour teindre les fibres kératiniques.
  22. Nécessaire pour teindre les fibres kératiniques, comprenant au moins une première préparation, contenant dans un véhicule acceptable sur le plan cosmétique,
    (A) au moins un produit précurseur de colorant,
    (C) au moins un tensio-actif glucidique, choisi dans le groupe qui est formé par
    - les alkyl- et alcényl-oligoglycosides et
    - les N-alkyl-polyhydroxyalkylamides d'acide gras et
    (D) au moins un agent réducteur, et une deuxième préparation, contenant dans un véhicule acceptable sur le plan cosmétique (B) au moins une enzyme qui peut catalyser l'oxydation des produits précurseurs de colorant, choisie parmi les laccases, (EC-N°1.10.3.2), les tyrosinases (EC-N°1.10.3.1), l'ascorbate oxydase (EC-N°1.10.3.3), les bilirubine oxydases (EC-N°1.3.3.5) ainsi que les phénol oxydases du type Acremonia, Stachybotrys ou Pleurotus.
EP01996352A 2000-11-20 2001-11-10 Colorant enzymatique Revoked EP1335696B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10057547 2000-11-20
DE10057547 2000-11-20
DE10116759 2001-04-04
DE10116759A DE10116759A1 (de) 2000-11-20 2001-04-04 Grundlage für enzymatische Färbemittel
PCT/EP2001/013025 WO2002039966A2 (fr) 2000-11-20 2001-11-10 Colorant enzymatique

Publications (2)

Publication Number Publication Date
EP1335696A2 EP1335696A2 (fr) 2003-08-20
EP1335696B1 true EP1335696B1 (fr) 2007-09-05

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JP (1) JP2004522709A (fr)
CN (1) CN1474682A (fr)
AT (1) ATE372106T1 (fr)
AU (2) AU2183702A (fr)
CA (1) CA2429408A1 (fr)
DE (1) DE50112973D1 (fr)
HU (1) HUP0301961A2 (fr)
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WO (1) WO2002039966A2 (fr)

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AU2001239217A1 (en) * 2000-03-17 2001-09-24 Novozymes A/S Method for dyeing dry hair
US6475274B1 (en) * 2000-03-24 2002-11-05 Thiele Kaolin Company Process for modifying particle size distribution

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CA2429408A1 (fr) 2002-05-23
HUP0301961A2 (hu) 2003-09-29
EP1335696A2 (fr) 2003-08-20
AU2002221837B2 (en) 2006-03-09
JP2004522709A (ja) 2004-07-29
AU2183702A (en) 2002-05-27
DE50112973D1 (de) 2007-10-18
US20040064901A1 (en) 2004-04-08
ATE372106T1 (de) 2007-09-15
WO2002039966A2 (fr) 2002-05-23
CN1474682A (zh) 2004-02-11
WO2002039966A3 (fr) 2002-12-19
PL361590A1 (en) 2004-10-04

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